Alkenylphenol-aldehyde resins



aldehyde resins.

United States Patent fitice 2,907,751 Patented Oct. 6, 1959 2,907,751,ALKENYLPHENOL-ALDEHYDE RESINS No Drawing. Application May 3, 1954Serial No. 427,386

This invention relates to a method for improving the properties ofresinsobtained by the condensation of an alkenylphenol with an aldehyde,and pertains more particularly to a process whereby the'alkenylphenol-aldehyde resin is heated with an alcohol in an acidic oressentially neutral medium.

In' copending applications, Serial Nos. 390,088, and

390,089, both filed November 3, 1953, now Patents Nos.

2,843,565 and 2,843,566, it is disclosed that alkenylphenols, such asmono-, di and trialkenylphenols condense with aldehydes, particularlyformaldehyde, in the presence of either an acidic or alkalinecondensation catalyst to yield resinous products which possess manyoutstanding properties. For example, the resins thus obtained producefilms which are fast drying and curing, and very light colored. Also,the resins possess outstanding solvent and alkali resistance andelectrical propertiesand are compatible with varnishes and drying oilsandother materials utilized in the preparation of coating compositions,such as 'vinyl resins, polyvinylacetal resins, epoxide resins, alkydresins and the like. Blends of alkenyl+ phenol-aldehyde condensationproducts With vinyl resins and with polyvinylacetal resins are extremelyuseful as sanitary liners for containers used in the packaging of foods,beverages, synthetic liquid detergents and similar materials.

phenols with aldehydes normally tend to be relatively in. stablematerials. This is particularly true of resins prepared from phenolitself, or alkyl substituted phenols, and to a much lesser degree istrue also of alkenylphenol- Also, the presence of even small quantitiesof unreacted phenols in the resin lowers to a considerable extent thecompatibility of the resin with other materials such as vinyl resins,polyvinylacetal resins and the like. i i

It has now been discovered that the disadvantages mentioned in theforegoing paragraph can be substantially overcome, and the usefulproperties of alkenylphenolaldehyde resins even further enhanced by arelatively simple procedure wherein the resin is heated with a hydroxylcontaining compound in an acidic or essentially neutral reacts with themethylol hydroxyl groups of the resin. The resulting resin, ordinarilyless viscous than the resin before the hydroxy compound is reactedtherewith, is considerably more stable than conventional phenol-aldehyderesins, is more compatible with other materials such as condensed withan aldehyde may vary p r However, resinsprepared by the condensation ofI medium. In this process some of the alcohol actually that phenolicresinscontaining one or more side chains on the phenolic nucleuspossessed relatively poor solvent resistance as a result of the presenceof the side chain. It has also been believed heretofore that theproperties of condensation products of aldehydes and phenols havingfewer than three reactive positions on the phenolic nucleus could not beimproved by heating with an alcohol in an acidic or essentially neutralmedium. However, the alkenylphenol or alkenylphenol mixtures which areutilized in the preparation of the resinous condensation prod uctsreacted with an alcohol in accordance with the present invention possesson an average only two reactive positions on the phenolic nucleus. It isalso believed surprising that the viscosity of the treated resin isactually lower than that of the untreated material since the literatureindicates that reaction of an alcohol with a phenolaldehyde resin inwhich the phenol contains no unsaturated side chain substituent causesbodying of the resin, that is, the viscosity of the resin actuallyincreases when the resin is heated with an alcohol.

The alkenylphenol-aldehyde resins which are treated with an hydroxylcompound in accordance with the present invention are ordinarilyobtained by condensing a mixture of alkenylphenols with an aldehyde inthe presence of an alkaline catalyst, although acidic catalysts may alsobe used. The mixture of alkenylphenols which is widely in composition.Ordinarily, the predominate component of the mixture is one or moremonoalkenylphenols, (including ortho and para-monoalkenylphenols), themonoalkenyl component constituting about 55 to 85 percent by weight ofthe total mixture. The balanceof the mixture (about 15 to 45 percent) iscomposed primarily of diand trialkenylphenols, although other phenolicmaterials, including polyphe nols such as alkane diand triphenols mayalso be present, depending upon the method by which the alkenylphenolmixture is prepared.

Mixtures of alkenylphenols of the type described in the foregoingparagraph are readily obtained by the methods described in copendingapplications, Serial No. 300,359, filed July 22, 1952, and Serial Nos.337,226, 337,227, 337,228 and 337,229, all filed February 16, 1953, thelatter two of which are now abandoned. The methods described in thesecopending applications involve the reaction of conjugated dienes withphenolic compounds in the presence of certain catalysts such as theFriedel-Crafts compounds. For example, thereaction product obtained bythe reaction of butadiene-l,3 with phenol in the presence of an aqueoussulfuric acid catalyst is generally composed of less. than about 15percent unreacted phenol, less than about 5 percent of ethers, 55 to 70percent of monobutenylphenols, and 15 to 50 percent of the higherboiling phenols including diand tributenylphenols and polyphenols.Ordinarily, the unreacted phenol and ethers will be removed from thereaction mixture by distillation before the condensation reaction withan aldehyde is carried out; however, this is not a critical expedientandthe condensation reaction takes place readily even though theunreacted phenolsand ethers are not removed. Mixtures containing smallerquantities of monoalkenylphenols and larger quantities of the higherboiling phenols, for

vinyl resins, alkyd resins and the like than is the untreated resin, andfilms prepared therefromtend to fabricate into severe angles orcurvatures more readily than the untreated resin films. Moreover, thereaction with an example, about50 percent monoalkenylphenols and 30 to50 percent of higher boiling phenols and the balance polyphenols andethers, may also be employed with good results, as may mixturescontaining no monoalkenylphenols.

. Also, the mixture may be composed entirely of ortho and hydroxycompound enhances the stability, compatibility and fabricationproperties of the resin without affecting the excellent solvent andalkali resistance or the other outstanding "properties possessed bythealkenylphenolaldehyde resins. This. is believed to be a ratherunexpected result, inasmuch as it has heretofore been thought 1para-monoalkenylphenols, and, in fact, excellent resins are a mixture isemployed. Mixtures of obtained when such alkenylphenols with minorquantities of other phenols containing nounsaturated side chain, such.as phenol, butylphenol, amylphenol audthe like may also be used.

It is to be understood that mixtures of alkenylphenols can also beobtained by other methods known to the art in addition to the reactionof conjugated dienes with phenolic compounds, and it is intended thatthe present invention include the use of any mixture of alkenylphenolsregardless of the method whereby it is obtained.

As illustrative of the alkenyl substituted phenolic compounds which arecondensed with an aldehyde to form the novel resins of the presentinvention there are set forth below the products of the reaction ofbutadiene-1,3 and phenol: H

A mixture of the above alkenylphenols forms excellent resins whencondensed with an aldehyde in the presence of an acidic or alkalinecatalyst.

v In general, he alkenylphenolic compounds which are condensed withaldehydes possess ,the structure Rn-Ar-(OH)n wherein Ar is an aromaticradical, R is alkenyl, cyclopentenyl, haloalkenyl, halocyclopentenyl,alkoxyalkenyl or alkoxycyclopentenyl, and n and n are whole numbers,ordinarily from 1 to 3. Preferably the sum of n and n is from 2 to 4.The alkenyl compounds of they above. structure are all readily obtainedby the reaction of phenolic compounds with conjugated dienes inaccordance'with the methods described in the copending applicationsreferred to hereinabove.

Whileit is preferred that a mixture of alkenylphenols be utilized inpreparing resins since sucha mixture is economically obtained by themethods described above, and does not require the relatively costlyseparation of the individual components of the mixture, it is. to beunderstood that if desired the monoakenylphenols or the diandtrialkenylphenols can be separated from the mixture and utilized in thepreparation of useful resins. The preferred alkenylphenol-aldehyderesins are those prepared from mixtures of the butenylphenols, includingorthoand para-Z-butenylphenols, di-Z-butenylphenols,

and tri-Z-butenylphenols. v

In preparing the, resins, any aldehyde-may be utilized. However,aldehydes containing only atoms. of carbon,

hydrogen and oxygen, and particularly formaldehyde, are. greatlypreferred. In placeof formaldehyde, a material which decomposes uponheating to yield formaldehyde,

' for example, paraformaldehyde or trioxymethylene, may

he utlhzed in the condensation reaction. '37 percent formaldehydesolution is .geuer llyl sd y An aqueous successfully,

1 4 Best results are obtained when an alkaline catalyst is employed incarrying out the condensation of a mixture of alkenylphenols or a singlealkenylphenol with an aldehyde. hydroxide, potassium hydroxide, bariumhydroxide, sodium carbonate, potassium carbonate, ammonia,hexamethylenetetramine and the like. Acidic catalysts such ashydrochloric acid, phosphoric acid, acetic acid, and oxalic acid mayalso be used.

The quantity of catalyst utilized may be varied considerably. Forexample, it is generally desirable that about one-fourth equivalent ofcatalyst be present for each equivalent of alkenylphenolic compounds.Based upon the total weight of the reactants, about 0.5 percent to about5.0 percent of the catalyst is used. Larger amounts of the catalyst-maybe utilized if desired.

Alternatively, the catalyst may be dispensed with entirely, althoughhigher reaction temperatures may then be required ,with attendantincrease in darkening of the resinous product.

The molar ratio of aldehyde-toalkenylphenols utilized in carrying outthe condensation reaction may be varied widely, and depends somewhat onwhether an acidic or alkaline catalyst is used. When an alkalinecatalyst is used, best results are obtained when about 2.0 moles of thealdehyde are utilized for each mole of the alkenylphenolic compounds inthe reaction mixture. However, the ratio maybe as low or lower than 0.5to 1.0 or as high or higher than 5.0 to 1.0. When the ratio is muchbelow the preferred 1.5. to 2.0 ratio the resinous product tends to behard. When the ratio is substantially above 2.0 to 1.0 good results areobtained but there is no economical advantage in utilizing such largeexcess of the aldehyde. Y I

On the other hand, when an acid catalyst is used, most useful resins areobtained when less than a mole of the:

aldehyde is employed for each moleof the alkenylphenolic component inthe reaction mixture, with about 0.8 mole of aldehyde to 1.0 mole of themixture of alkenylphenolic compounds being preferred. However,

the ratio may be as low or lower than 0.5 to 1.0 or as high or higherthan 5.0 to 1.0. When the ratio is substantially above 1.5 to -1.0 noadvantage is obtained,

and in fact, gels, rather than hard resins, may be formed.

Consequently, the use of such an uneconomical excess and cooling isapplied as needed to keep the temperature 7 below about 35 C. Careshould be taken to keep traces of air out of the reactorat all timesduring thtCOIldensation. Stirring is continued; for about 48 hours. atroom temperature.

At the end of this time the reaction mixture is care fully acidified toa'pI-I of about-5.0 with a mineral acid such as hydrochloric 'acid,phosphoric acid or sulfuric acid, or a carboxylic acid such as aceticacid .or propionic acid. Two layers are formed, a water layer and analkenylphenolic resin layer. The water layer is drawn offand the waterinsoluble layer of resin is'water washed 4 or 5 times.

' about 0.1 percent by Weight of a material such as an At this point itis advantageous to add aminotetracarboxylic acid which forms a complexwith any iron in the reaction mixture. The presence of uncomplexed ironis likely to cause darkeningof the prodnot. The resin is thendehydrated'by vacuum stripping at steam, temperatures and at a pressureof about 20 mm. to 55. mm. Alternatively, the water can beremov'ed byadding a solvent and then carrying out an azeotropic dist l a on. I

Suitable alkaline materials include sodium ILA.

A preferred method from the standpointof simplicity is to acidity,separate the resin layer, anddrybthe resin layer by blowing withan inertgasat 220 F. to 230 F. The resin is thinned witha suitable solvent;.-andthe salt removed by filtration.

While the above described method for carrying out the condensation ispreferred, particularly when the alkenylphenol mixture is a mixture ofbptenylphenols, other methods of carrying out the condensation, forexample, simply by admixing the. reactants and catalyst and allowing-themixture {to stand at room temperature for about 4 hours, or: bymaintaining the reaction mixture at temperatures as highas 1009 C. or;higher, may also be utilized. In the event that highertemperatures areutilized the condensation will, of course, require less time than when,the condensation is carried out at room temperature, y hi y While theresins obtained by the alkaline condensation of a mixture ofalkenylphenols withan aldehyde sueh as. formaldehyde are generallyrecovered as viscous-liqui ds, it is also possible. to. obtain hardresinous materials by condensing equimolar quantities of alkenylphenolsand aldehyde in the presence of an alkaline catalyst and then acidifyingthe :reac tion mixture. to a pH of about. 2.0, The resulting hardmaterials are especially useful as varnish resins. ",i a i 1: U a a iThe acid catalyzed condensation reaction; is best oarried out by firstadmixing the formaldehyde, or formaldehyde producing substance, with themixture of alkenylphenols andthe acidiccatalyst, Theresulting mixtureisthen heated to atemperature o aboutfihf'pftd 150. C for about 2 to 3hours,.atterfwhich,tlie 'water present in the reaction mixtureisstripped off by distillation at reduced pressure, leaving thedesiredresinfas a hard, grindable material. The reaction .i'ean,however, also'be carried out simplyQby" admixing the reactants. and theacidiccatalyst and allowingthe mix-ture to stand at roam temperature for48 hours, or; by maintaining. the mac tion mixture at temperatures evenhigher. 150 C. v In accordance with the present invention a resinoucondensation product prepared. in the. foregoing. manner is heated withan hydroxyl compoundin an acidicor essentially neutral medium. Thenatureof the hydroxyl compound .utilized is not critical and may bevarie-dconsiderably. Preferably, however, it an. of the structure ROH, whereinR is. an alkyl radical such has methyl, ethyl, propyl, buty-l, amyl, orZ-ethylhexyl. Bu tyl alcohol and 2 -ethyl-hexanol-1 are especiallyuseful for this purpose Other alcohols which may be used include castoroil, butane dio1'-1,4, soya alcohols, allyl -.alcohol,,ethy1ene glycol,alkyd resins containing free hydroxyl groups, and others. The amountofialcohol utilized in the process may also be varied widely, altho'ughin general it is. desired that it .beutilized in an amount about equalto the, quantity of resin being treated; Larger or smaller quantitiesmay be employed if desired.

It has been found thatvbest resultsfare .ob,tained.when the reaction iscarried to a stage such that-the quantity of alcohol which. actuallyreacts withiherein isfr'om about to. 30 percent. by weight. The degreeof reactionhobtained can readily 'be rcalculated by determining the"solids content of the resin before and after treatment, with thediflerence indicating the amount of alcohol which 7 has reacted with theresin.

As indicatedhereinaboye,,the heating is carried out in anacidid'iir'essentially neutral medium," that is, at a pH of 7.0 orbelow. Preferably, the p l-Igduring th e hea tcontrolled fby adjustmentofif the pH,

ing process ismaintainedat ab ..3.0 10:50.] The amount v of alcohol;which reacts with the resin can'be accurately, I the reaction rateincreasing as the pHjof the'mediuni is decreased. The a desired canreadily be obt'ainedfby initially acidity- F ing theyuntreated resinwithi'a mineral acid such as sul-.

furic acid,-hydrochloric acid or phosphoric acid, or an and xylene;

organic carboxylicacid such as acetic acid, propionic acid, oxalicacid,,or maleic acid.

The process is readily carried out simply by admixing the acidifiedresinous condensation product with the desired quantity of hydroxylcompound; and then heating at reflux temperature for a period of about 3to 4 hours, after which the resin is recovered by filtering or otherconventional means of separation. This simple procedure is preferred;however, generally equivalent results are obtained if the hydroxylcompound is added to the mixture of the alkenylphenol and aldehydeduring the condensation reaction, although it is more difiicult to contol the degree. of reaction by this latter procedure. TheIreaction alsotakes place at temperatures lower than those required to obtain reflux,although the rate of reaction islikely to be slower at thelowertemperatures. Theifollowing examples illustrate in detail thepreparation of resinous condensation products from alkenylphenols andaldehydes, and the reaction of the resulting resins with an alcohol inaccordance with the present invention. The examples are not, however,intended to lirni-tfthe invention, inasmuch as there are, of course,numerous possible variations and modifications.

Example I One hundred forty-eight parts of a mixture of mono-.butenylphenolsloand p-monobutenylphenols) andflQ parts of sodiumhydroxide in parts of water were mixed under a nitrogen atmosphere withsuflicient cooling to keep .the temperature below about 35 C. When ahomogeneous solution was obtained, 163 parts of 37 percent formalin,methanol free, containing 60 grams (2 moles) of solid formaldehyde wereadded at a moderate rate, cooling was continued to keep the temperaturebelow about 35 C. Stirring was continued for about 48 hours at roomtemperature. At the end of this time the reaction mixture was acidifiedto a pH of 5.0 with a mixture of concentrated hydrochloric acid andwater (50 percent acid and 50 percent water) and the resulting waterinsoluble layer of the resin was washed 4 times with lukewarm water. Theresin was then dehydrated by vacuum stripping at steam temperaturesunder 20 mm. to 50 mm. pressure; The yield based on the quantity ofalkenylphenols utilized was percent, the viscosity at 25 C. wasW to Z(Gardner), and the resulting resin was completely miscible with ethanol,butanol, toluene,

Example .11

Example I was repeated using each of the followingformaldehyde:butenylphenol ratios: 0.8:1, 1:1, 2:1,and 4: 1. In each runa resin was obtained which gave light colored, fast curing films andwhich was compatible with drying oils, varnishes, alkyd resins and agreat many other film forming materials.

Example 111 Several different aldehydes were condensed with mixedbuteny-lphenols, including mono-, diand tributenylphenols, The aldehydeutilized, the catalyst concentration, the mole ratio of aldehyde tobutenylphenol, the reaction time and temperature (degrees centigrade)are set forth in the following table:

Ratio of l Aldehyde Reaction Time Aldehyde Catalyst to Mixed andTemperature Butenyl- (Degrees, O.)

phenols Furfural ,3%,Sod ium Hydroxide 1:1 25 C.48 hrs. Urotonaldehyde-4% Sodium Hydr0xide 4:1 25 O.48 hrs. Acetaldehyde... 31% SodiumHydroxlde4:1 25 C.48 hrs.

- it was allowed to stand for 43 hours.

Example IV Thefollowing materials were changed into a glass linedreactor: 7

24.6 pounds mixedbutenylphenols (monobutenylphenols,

diandtributenylphenols) 27 .0 pounds formalin solution (37 percentfonnal'dehyde) 1.7 pounds sodium hydroxide 1.7 poundswater 0.12 poundsodium hydrosulfite 1 The resulting mixture was cooledto 75 Fqto 80 F.and the reaction mixture agitated for 5 hours after which The reactionmix ture was then acidified to a pH of 5.0 with 68 percent sulfuricacid, and allowed to stand until a water layersettled out. The waterlayer w'as then drawn 011 and discarded. To the wet resin (36.25 pounds)0.04 pound of an aminotetracarboxylic acid known commercially asSequestrene AA was added. The resin was then heated to 220 F. andstripped with an inert gas (nitrogen) until a Gardner viscosityo-f W at75 percent solids in n-butanol was reached. The resin was then thinnedwith pounds of n-butanol and filtered at 110 F. The following is theanalysis of the final material:

Weight per gallon 8.45 pounds. I Solids 66.2 percent at 110 C..Viscosity Q to R (Gardner).

Eighty-five parts ofthe resin thus prepared was blended with parts byweight of polyvinylbutyral and roller coated on tin plate and cured at350 F. for minutes. The resulting film was of a thickness such thatthe'film weighed 16 mgm./ 4 square inches, and was light colored,mar-resistant and insoluble in acetone.

Example V One hundred sixty-two grams (1 mole) of a mixture ofpentenylphenols was placed in a glass lined reactor fitted with acondenser. Sixty-four and eight-tenths grams of formalin solution (0.8mole formaldehyde) were then added to the pentenylphenols at atemperature. of 24 C. Five cc. of concentrated hydrochloric acid wereadded slowly through the condenser, the temperature rising to 28 C.during the addition of the acid. The reaction mixture was then heated at95 C. for 2 hours, during a which time it was continuously agitated. Thereaction Example VI Example V was repeated except that l'mole of amixture of cyclopentenylphenols was substituted for the mixture ofpentenylphenols utilized in Example V. One

' time.

hundred fifty-nine and two-tenths grams of a gum-like resin having 95.6percent of solids were obtained. On baking at 175 C for 1% hour'sa veryhard, grindable resin was obtained. 1

Example VII 7 Fifteen hundred fifty-eight and six-tenths grams ofbutenylph'enobjformaldehyde resin prepared according to the method ofExample IV was acidified with phosphoric acid to a pH of 6.0. A secondchange of 1382 grams of abutenylphenolformaldehyde resin also preparedaccording to the method of Example IV, was acidified with phosphoricacid to a pH'of 3.4. Butyl alcohol was present in each of these chargesin anamount of 25 percent by weight.

Both charges were then refluxed for 2% the pot temperature reaching 132C. at the end of this By determining the solids content of each resinbefore and after the reaction, it was determined that in th'exfirstcharge, the butyl alcohol had reacted to an extent of 12.1 percent ofthe solids and in the second charge 17.7 percent, indicating that thereaction rate increases as the pH of the refluxing medium is lowered.

The resins thus prepared were found to be extremely 0 Example VII Iafter 13 hours or reflux a percent solids of 58.2. The

percent butylation was 14. The resulting 'resinwas clear and extremelylight colored, and when parts thereof were blended with'15' parts ofpolyvinylbutyral a composition was obtained which produced films ofoutstanding alkali and solvent resistance. The composition was usetul asa coating composition for containers used in the packaging of'food's,beverages, synthetic liquid-detergents and the like. v i r V ExamplesIXto XV I Inth'e following 'exampels, a number of different alcohols wereheated with butenylphenol-formaldehyde resins (prepared according to themethod of Example IV and distilled to remove any solvent present). In.each example, grams of butcnylphenol-formaldehyde resin and 0.2 gram ofmaleic-anhydride were admixed with the alcohol. In Examples IX throughXIV 100 grams of toluene were added and the mixture refluxedazeotropically'for 3 hours (in Example XI for-2 hours) in Example XV,the toluene-was omitted and the mixture heated to refluxr The specificalcohol utilized and the quantity thereof, the yield, the percentsolids, the Gardner color and viscosity are set forth in theaccompanyingtable:

.Oharge. Example Yield Percent Color Viscosity I (Parts) Solids (Gerd-(Gardner) Parts Alcohol Parts ner) Toluene Ale hol Butyl'alcbh01 25'201. 1 50.8 7 A- Castor oil alcohol 25-, 226.0 49.1 j Jfi' E-F Butanedi0l-1, 4. 25 227.6 46. 2 6 A- 25' 200.2 54.9. G 7.4- 25 226.4 {46.5. 6A-'- 25 225.7 46.6" 6 A- 100 202.4 48.5 7-8 1A.-

hours with 7 .Five hundred gramsof a butenylphenobformaldehyde I resinprepared according to the method of Exam'pleIV (except that thewet'resinwas used after separation of 9. The resinous composition obtained in theabove examples was in each instance more compatible with otherresinouslmaterials such as vinyl resins, alkyd resins and the like thanthe butenylphenol-formaldehyde resin before reaction with the alcohol.,The final resinous products were also more stable than abutenyl-phenol-aldehyde resin which had notbeen reacted with an alcohol.

Example X VI Twenty two hundred seventy seven grams of abutenylphenol-formaldehyde resin (prepared according to the method ofExample IV), 732 grams of 2-ethyl hexanol-l and 400 grams of toluenewere admixed and the pH of the mixture lowered to 4.5 by addingphosphoric acid. The resulting mixture was then heated and the waterremoved using a toluene filled separator. After the greater part of thewater was removed, the temperature rose steadily to 120 F. More toluenewas added in order to keep the temperature at about 120 F. The batch wasthen retiuxed for 3 hours at 120 F. The toluene was then distilled oifuntil a flask temperature of 140 C. was reached. The resulting resin wastreated with 0.5 percent triethanolamine, cooled slightly and filteredunder a vacuum. Twenty nine hundred ninety four grams of a resin havinga solids content of 71 percent, a viscosity of G-H (Gardner), a weightper gallon of 8.39, and a Gardner color of 6-9 was obtained. It wasdetermined that the 2-ethyl hexanol-l had reacted with the resin in anamount of 27.4 percent based on the charged solids.

The resulting resin was blended with polyvinylbutyral, thepolyvinylbutyral being present in an amount of about 10 percent byweight. The composition was baked for 10 minutes at 390 F. on tin plateto give a film having a thickness such that the film weighed 10 mgm./4square inches. The film fabricated well and was resistant to the actionof chemicals.

A second sample of the resinous product was blended with a hydroxylmodified copolymer of vinyl acetate and vinyl chloride, thebutenylphenol-formaldehyde resin bemg present in an amount of 90 percentby weight, to give a composition which was baked for 10 minutes at 390F. on tin plate. The film fabricated well and was extremely resistant tothe action of chemicals.

Example XVII Samples of the resinous condensation product of Example VHIwere blended with an oleoresinous varnish, thebutenyl-phenol-fdrmaldehyde resin being varied in an amount from 15 to50 percent by weight of the total composition. Thebutenyl-phenol-formaldehyde resin product was compatible with theoleo-resinous varnish over the entire weight percent range and theresulting compositions gave compatible films which fabricated well andwhich did not show any signs of fracture when immersed for 5 minutes ina copper sulfate solution. Also, the resinous product when pigmentedwith materials such as zinc oxide or titanium oxide gave good resistanceat processing temperatures in the presence of meat and other foodproducts.

A butenylphenol-formaldehyde resin, similar in all re spects to theresinous product of Example VIII except that it was not reacted withbutyl alcohol, was found to be compatible with the same oleoresinousvarnish only in amounts below 25 percent by weight. It is apparent,therefore, that the compatibility of alkenylphenol-aldehyde resins withvarnishes is greatly increased when the resin is first reacted with anhydroxyl compound.

Example X VIII An alkyd resin was prepared by admixing 235.5 grams ofcrystallized cottonseed fatty acids, 184 grams of phthalic anhydride,and 118 grams of glycerol, and heating the resultant mixture in xyleneunder an azeotropic reflux at 180 C.' The temperature was then loweredto 150 C. and 500 grams of butenylphenol-formaldehyde resin (70 percentsolids) and 0.6 gram of ethylenediamine tetraacetic acid were added. Thetemperature was then raised to 200 C. until a Gardner viscosity of X wasobtained, and the resulting product was thinned with xylene.

With no added modifiers the resin prepared" according to the abovemethod was stripped out from a butanol solution onto iron plate to giveafilm having a thickness of approximately 12 mgm. 4 square inches ofarea. The baked film (10 minutes at 390 F.) was clear and level withgood flow out properties and fabricated into a container closure capvery readily, giving no signs of fracture in a 5 minute immersion incopper sulfate solution. The film did not blush when. immersed in waterfor 1 hour at 250 F.

Example XIX In order to determine the stability of alkenylphenolaldehyderesins which had been reacted with a hydroxyl compound in accordancewith the present invention as compared to the untreatedalkenylphenohaldehyde resins, a number of preparations of both types ofresins were carried out and the resulting resinous products weremaintained at a temperature of F. at varying pH values and observeddaily to determine how long the sample re mained clear and bright. Thematerial was classed as being no longer stable when it became hazy andwater began to condense therefrom. The pH at which the resin wasmaintained and the number of days required for the resin to becomeunstable are recorded below:

Days at 150 F. Before Becoming Hazy 21 21 21 Over 50 Over 50 Over 50Untreated butenylphenolformaldehyde resin...

Butenylphenol-formaldehyde resin reacted with butan n1 Moreover, whenother alkenylphenols are substituted for the butenylphenols andpentenylphenols in the above examples, good results are obtained.Similarly, when other methods of carrying out the reaction of the resinwith the alcohol are employed, compatibility and stability of theresulting materials are considerably improved.

It is apparent from the foregoing description that the process of theinvention provides an economical and useful method for improvingstability and compatibility characteristics of resins prepared by thecondensation of alkenylphenols with aldehydes. It will also be apparent,therefore, that various embodiments of the invention, in addition tothose specifically disclosed, may be provided Without departing from thespirit and scope of the invention as defined in the appended claims.

We claim:

1. A method of improving the stability, compatibility, and fabricationproperties of an alkaline catalyzed resinous condensation product offormaldehyde and a mixture of butenylphenols consisting ofmonobutenylphenols, dibutenylphenols, and tributenylphenols saidresinous condensation product being characterized by having methylolradicals attached to carbon atoms of the phenolic rings, which comprisesheating a mixture of said resinous condensation product and an aliphaticmonohydric alcohol containing from 1 to about 8 carbon atoms, whilemaintaining the pH of the reaction mixture below about 7.0 for a periodsuch that about 10 percent to 30 percent of the hydroxyl groups of saidmethylol radicals of the resin are reacted with said alcohol.

2. The method of claim 1 wherein the reaction mixture is heated toreflux temperature.

3. The method of claim 2 wherein the pH is maintained within the rangeof about 3.0 to 6.0.

4. The method of claim 3 wherein the alcohol is butanol.

'11 5. The method of claim 3 whe r ein the alcohol is 2- ethylhexanol-l.

6. A resinous product prepared according to the meth- 0d of claim 1.

References Cited in.the file of this patent UNITED STATES PATENTSDykstr-a June 25, 1935 Honel et a1 May 20, 1941 Jones Mar. 4, 1952 Younga Oct. 27, 1953 FOREIGN PATENTS Austria Apr. 25, 1939 Great Britain July6, 1922 Great Britain Aug. 21, 1939 France Oct. 3, 1951

1. A METHOD OF IMPROVING THE STABILITY, COMPATIBILITY, AND FABRICATIONPROPERTIES OF AN ALKALINE CATALYZED RESINOUS CONDENSATION PRODUCT OFFORMALDEHYDE AND A MIXTURE OF BUTENYLPHENOLS CONSISTING OFMONOBUTENYLPHENOLS, DIBUTENYLPHENOLS, AND TRIBUTENYLPHENOLS SAIDRESINOUS CONDENSATION PRODUCT BEING CHARACTERIZED BY HAVING METHYLOLRADICALS ATTACHED TO CARBON ATOMS, OF THE PHENOLIC RINGS, WHICHCOMPRISES HEATING A MIXTURE OF SAID RESINOUS CONDENSATION PRODUCT ANDALIPHATIC MONOHYDRIC ALCOHOL CONTAINING FROM 1 TO AB OUT 8 CARBON ATOMS,WHILE MAINTAINING THE PH OF THE REACTION MIXTURE BELOW ABOUT 7.0 FOR APERIOD SUCH THAT ABOUT 10 PERCENT TO 30 PERCENT OF THE HYDROXY GROUPS OFSAID METHYLOL RADICALS OF THE RESIN ARE REACTED WITH SAID ALCOHOL.